Monoazo blue disperse dye compounds and methods for dyeing or printing hydrophobic fiber materials using the same

ABSTRACT

A monoazo compound of the following formula(I): ##STR1## wherein R 1  represents a hydrogen atom or a chlorine atom; R 2  represents a phenyl group or an alkyl group which is unsubstituted or substituted; R 3  is a hydrogen atom or C 1  -C 4  alkoxy; and R 4  and R 5  represent a hydrogen atom, an allyl group, a tetrahydrofurfuryl group, or an alkyl group which is unsubstituted or substituted by a chlorine atom, a cyano group, an alkoxy group, a hydroxy group, a phenoxyalkoxy group, a phenoxy group, a phenyl group, a benzyloxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, an alkanoyloxy group, a benzoyloxy group, a phenoxycarbonyloxy group, an alkanoyl group, an alkoxyalkoxycarbonyl group, tetrahydrofurfuryloxy carbonyl group or an alkoxyalkoxy group; provided that R 4  and R 5  are not hydrogen atoms or a substituted alkyl group simultaneously; and 
     a method for dyeing or printing a hydrophobic fiber material using the monoazo compound.

The present invention relates to a monoazo compound useful for dyeing orprinting hydrophobic fiber materials and capable of giving a bright bluedyed product excellent in various properties such as washing fastness.

So far, various kinds of monoazo type blue disperse dyes for hydrophobicfiber materials such as polyester have been proposed. For example, amonoazo type blue disperse dye represented by the following formula:##STR2## is described in JP-A-48-84120. However, the monoazo type bluedisperse dye is not sufficient in brightness of color.

In recent years, in order to cope with a consumers' trend toward highergrade clothing, dyed or printed products mainly comprising hydrophobicfiber materials dyed or printed with disperse dye have come to besubjected to various after-finishing treatments such as softening,antistatic and feel-improving finishing to give higher added values.These after-finishing treatments are, however, carried out at hightemperatures which often cause dye bleed so that the dyed or printedproducts deteriorate in their wet fastness, particularly washingfastness.

Under such circumstances, developments of bright blue disperse dyesexcellent in dyeability as well as in various fastness such as lightfastness, sublimation fastness and wet fastness have been desired.

Inventors of the present invention have conducted extensive studies todevelop such dyes and, as a result, have found that certain specificmonoazo compounds are very suitable for the above-mentioned objects. Thepresent invention has thus been accomplished.

The present invention provides a monoazo compound represented by thefollowing formula(I): ##STR3## wherein R₁ represents a hydrogen atom ora chlorine atom; R₂ represents a phenyl group or a straight chain orbranched chain alkyl group which is unsubstituted or substituted; R₃ isa hydrogen atom or C₁ -C₄ alkoxy; and R₄ and R₅, which are same ordifferent, represent a hydrogen atom, an allyl group, atetrahydrofurfuryl group, or a straight chain or branched chain C₁ -C₆alkyl group which is unsubstituted or substituted by one or twosubstituents selected from a chlorine atom, a bromine atom, a cyanogroup, an alkoxy group, a hydroxy group, a phenoxyalkoxy group, aphenoxy group, a phenyl group, a benzyloxy group, an alkoxycarbonylgroup, an alkoxycarbonyloxy group, an alkanoyloxy group, a benzoyloxygroup, a phenoxycarbonyloxy group, an alkanoyl group, analkoxyalkoxycarbonyl, tetrahydrofurfuryloxy carbonyl group and analkoxyalkoxy group; provided that R₄ and R₅ are not simultaneouslyhydrogen atoms, and that R₄ and R₅ are not simultaneously straight chainor branched chain C₁ -C₆ alkyl groups which are substituted by one ortwo substituents selected from a phenoxyalkoxy group, a phenoxy group, aphenyl group, a benzyloxy group, a benzoyloxy group and aphenoxycarbonyloxy group.

The present invention also provides a method for dyeing or printinghydrophobic fiber materials using the monoazo compound.

R₁ in the formula(I) is preferably a hydrogen atom. R₂ in the formula(I) is preferably a phenyl group or a straight chain or branched chainC₁ -C₅ alkyl group unsubstituted or substituted by a chlorine atom, acyano group, a C₁ -C₃ alkoxy group or the like, and more preferably aphenyl group or an unsubstituted C₁ -C₄ alkyl group such as a methylgroup or an ethyl group. R₃ in the formula(I) is preferably a hydrogenatom or a C₁ -C₃ alkoxy group such as a methoxy group or an ethoxygroup, and more preferably a hydrogen atom.

The straight chain or branched chain alkyl groups denoted by R₄ or R₅ inthe formula(I) may be unsubstituted alkyl groups, alkyl groupssubstituted by one substituent or alkyl groups substituted by twosubstituents.

Examples of the unsubstituted alkyl groups denoted by R₄ or R₅ include

a methyl group, an ethyl group, an n-propyl group, an i-propyl group, ann-butyl group, an n-pentyl group and an n-hexyl group.

Examples of the alkyl groups denoted by R₄ or R₅ and substituted by onesubstituent include

a chlorosubstituted alkyl group such as 3-chloropropyl group and2-chloroethyl group; a bromosubstituted alkyl group such as3-bromopropyl group and 2-bromoethyl group; a cyanosubstituted alkylgroup such as 2-cyanoethyl group; a (C₁ -C₄ alkoxy)substituted alkylgroup such as 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropylgroup and 3-ethoxypropyl group; a hydroxysubstituted alkyl group such as2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and4-hydroxybutyl group; a phenoxyalkoxy substituted alkyl group such as2-(2-phenoxyethoxy)ethyl group; a phenoxysubstituted alkyl group such as2-phenoxyethyl group; a benzyloxy substituted alkyl group such as2-benzyloxyethyl group; a phenylsubstituted alkyl group such asphenethyl group and benzyl group; a C₂ -C₅ alkanoyloxy ethyl group suchas 2-acetoxyethyl group, 4-acetoxybutyl group and 2-propionyloxy ethylgroup; a benzoyloxy substituted alkyl group such as 2-benzoyloxyethylgroup; a C₂ -C₅ alkoxycarbonyl(in this specification, "C₂ -C₅alkoxycarbonyl" means "carbonyl substituted by C1-C4 alkoxy) substitutedalkyl group such as 2-methoxycarbonyl ethyl group and 2-ethoxycarbonylethyl group; a C₂ -C₅ alkoxycarbonyloxy substituted alkyl group such as2-methoxycarbonyloxy ethyl group and 2-ethoxycarbonyloxy ethyl group; aphenoxycarbonyloxy substituted alkyl group such as 2-phenoxycarbonyloxyethyl group; a C₂ -C₅ alkanoylsubstituted alkyl, group such as2-acetylethyl group and 2-propionylethyl group; an alkoxyalkoxycarbonylsubstituted alkyl group in which each of the alkoxy groups has one tofour carbon atoms such as 2-(2-methoxyethylcarbonyl)ethoxy group; analkoxyalkoxy substituted alkyl group in which each of the alkoxy groupshas one to four carbon atoms such as 2-(2-methoxyethoxy)ethyl group,2-(2-ethoxyethoxy)ethyl group and 2-(2-butoxyethoxy)ethyl group; and atetrahydrofurfuryloxy carbonyl substituted alkyl group such astetrahydrofurfuryloxy carbonyl ethyl group.

Among the above-mentioned alkyl groups substituted by one substituent, acyanosubstituted alkyl group such as 2-cyanoethyl group; a C₁ -C₄alkoxysubstituted alkyl group such as 2-methoxyethyl group,2-ethoxyethyl group, 3-methoxypropyl group and 3-ethoxypropyl group; ahydroxysubstituted alkyl group such as 2-hydroxyethyl group,2-hydroxypropyl group, 3-hydroxypropyl group and 4-hydroxybutyl group; aphenoxyalkoxy substituted alkyl group such as 2-(2-phenoxyethoxy)ethylgroup; a phenoxysubstituted alkyl group such as 2-phenoxyethyl group; aphenylsubstituted alkyl group such as phenethyl group and benzyl group;a C₂ -C₅ alkanoyloxy ethyl group such as 2-acetoxyethyl group,4-acetoxybutyl group and 2-propionyloxy ethyl group; a benzoyloxysubstituted alkyl group such as 2-benzoyloxyethyl group;:a C₂ -C₅alkoxycarbonyl substituted alkyl group such as 2-methoxycarbonyl ethylgroup and 2-ethoxycarbonyl ethyl group; a C₂ -C₅ alkoxycarbonyloxysubstituted alkyl group such as 2-methoxycarbonyloxy ethyl group and2-ethoxycarbonyloxy ethyl group; a phenoxycarbonyloxy substituted alkylgroup such as 2-phenoxycarbonyloxy ethyl group; an alkoxyalkoxysubstituted alkyl group in which each of the alkoxy groups has one tofour carbon atoms such as 2-(2-methoxyethoxy) ethyl group,2-(2-ethoxyethoxy)ethyl group and 2-(2-butoxyethoxy)ethyl group; and atetrahydrofurfuryloxy carbonyl substituted alkyl group are preferred.Among the preferred examples, particularly preferred examples includethe above-mentioned cyanosubstituted alkyl, C₁ -C₄ alkoxysubstitutedalkyl, hydroxysubstituted alkyl, phenoxysubstituted alkyl, C₂ -C₅alkanoyloxy substituted alkyl, C₂ -C₅ alkoxycarbonyl substitutedalkyl,₋₋ C₂ -C₅ alkoxycarbonyloxy substituted alkyl, alkoxyalkoxysubstituted alkyl in which each of the alkoxy groups has one to fourcarbon atoms and tetrahydrofurfuryloxy carbonyl substituted alkylgroups.

Examples of the alkyl groups denoted by R₄ or R₅ and substituted by twosubstituents include 3-phenoxy-2-hydroxypropyl group,3-methoxy-2-hydroxypropyl group, 3-butoxy-2-hydroxypropyl group,3-methoxy-2-acetoxypropyl group and 3-ethoxy-2-acetoxypropyl group.

Among compounds of the present invention, compounds of formula (I)wherein

one of R₄ and R₅ is a cyanosubstituted alkyl, C₁ -C₄ alkoxysubstitutedalkyl,hydroxysubstituted alkyl, phenoxysubstituted alkyl, C₂ -C₅alkanoyloxy substituted alkyl, C₂ -C₅ alkoxycarbonyl substituted alkyl,C₂ -C₅ alkoxycarbonyloxy substituted alkyl, alkoxyalkoxy substitutedalkyl in which each of the alkoxy groups has one to four carbon atoms ortetrahydrofurfuryloxy carbonyl substituted alkyl group, and another isan unsubstituted alkyl group;

R₁ is a hydrogen atom;

R₃ is a hydrogen atom, a methoxy group or an ethoxy group;

and R₂ is a methyl group or an ethyl group are preferred.

The monoazo compound of formula (I) can be produced, for example, by adiazotization of a 2-amino-3-cyano-5-nitrothiophene represented by thefollowing formula (II): ##STR4## wherein R₁ is as defined aboveaccording to a conventional method, followed by a coupling reaction ofthe diazonium compound thus obtained with a3-N-substitutedamino-alkylsulfonyl aminobenzene compound or a3-N-substitutedamino-phenylsulfonylamino benzene compound represented bythe following formula (III): ##STR5## wherein R₂, R₃, R₄ and R₅ are asdefined above. The compound of formula(II),2-amino-3-cyano-5-nitrothiophene, is a known compound which can beproduced by a method described, for example, in JP-A-48-84120,JP-B-55-18710 or JP-A-6-25220.

The compound of formula(III), a 3-N-substituted amino-alkylsulfonylaminobenzene compound or a 3-N-substitutedamino-phenylsulfonylaminobenzene compound, can be produced by reacting

a compound represented by the following formula(IV): ##STR6## wherein R₃is as defined above, a compound represented by the following formula(V):

    R.sub.4 --X.sub.1

wherein R₄ is as defined above and X₁ represents a leaving group whichis substitutable by a nucleophile, such as a chlorine atom, a bromineatom, an iodine atom, a p-toluenesulfonyloxy group, a benzenesulfonyloxygroup and the like, and

a compound represented by the following formula(VI):

    R.sub.5 --X.sub.2                                          (VI)

wherein R₅ is as defined above and X₂ represents a leaving group whichis substitutable by a nucleophile, such as a chlorine atom, a bromineatom, a iodine atom, a p-toluenesulfonyloxy group, a benzenesulfonyloxygroup and the like

to obtain a compound represented by the following formula(VII): ##STR7##wherein R₃, R₄ and R₅ are as defined above; followed by hydrolyzing theresulting reaction compound of formula(VII) to obtain a compoundrepresented by the following formula(VIII): ##STR8## wherein R₃, R₄ andR₅ are as defined above; and, then, by reacting the resulting reactioncompound of formula(VIII) with a compound represented by the followingformula(IX):

    R.sub.2 --SO.sub.2 Cl                                      (IX)

wherein R₂ is as defined above.

There are various other known methods for producing a compound of theformula(VII) from a compound of the formula(IV). A method described in"Grundlagen der Synthese von Zwischen-produkten und Farbstoffen,Akademie-Verlag Berlin 1966, pp 577-631, N. N. Woroshzow can bementioned as an example of them.

The monoazo compound of formula(I) is useful for dyeing and printinghydrophobic fiber materials, particularly for polyester fiber materials.A dye dispersion can be obtained by finely dispersing the monoazocompound according to a conventional method together with an appropriatedispersing agent such as naphthalenesulfonate-formalin condensate andligninsulfonic acid in an aqueous medium. The dye dispersion thusobtained can be used as it is, i.e. in the form of liquid, or in theform of a powder obtained, for example, by spray drying. For dyeing,particularly for a high temperature dyeing method, a monoazo compound ofthe present invention is dispersed in an aqueous medium to obtain a dyedispersion, other components such as a pH adjusting agent or adispersion level dyeing agent are added to the dye dispersion, ifrequired, and, then, a hydrophobic fiber material is dipped into thedispersion to carry out dyeing. When polyester fiber material is used,dyeing is carried out under an elevated pressure usually at atemperature not lower than 105° C., preferably 110°-140° C.Alternatively, dyeing can be carried out in the presence of a carriersuch as o-phenylphenol, trichlorobenzene and methylnaphthalene at arelatively high temperature, for example, in boiling water. Furthermore,such a dyeing process, so-called thermosol dyeing process, in which adye dispersion is padded onto a cloth, followed by a steaming or adry-heating at a temperature of 100° C. or higher may be carried out.

For printing, a dye dispersion may be kneaded with a suitable paste, andthe resulting color paste may be padded on a cloth and then subjected toa steaming or thermosol treatment. Solvent dyeing in which an organicsolvent such as trichloroethylene or perchloroethylene is used as dyeingmedium can also be conducted.

For dyeing or printing hydrophobic fiber materials with the monoazocompound of formula(I), another dye may be blended with the monoazocompound and various kinds of additives may be added during preparationof the dye dispersion.

If necessary, dyed products obtained by dyeing or printing with themonoazo compound of formula(I) may be subjected to various kinds ofafter-finishing treatments such as softening, water repelling,feel-improving, antistatic and sanitary finishing.

Bright blue dyed products obtained by dyeing or printing hydrophobicfiber materials, such as polyester fiber materials, using monoazocompound of the formula(I) are excellent in various fastness such aslight fastness, sublimation fastness and wet fastness. Particularly,they have a characteristic that the washing fastness does notdeteriorate even after an after-finishing treatment or heat settreatment. For example, washing fastness of a polyester fiber materialdyed in deep color(JIS 2/1 depth) with the monoazo compound offormula(I) and then subjected to a heat set treatment is much superiorto that of a dyed product dyed with a conventional dye even when testedaccording to conditions corresponding to home washing(eg. AATCC IIAmethod). Using the monoazo compound of formula(I), very fine-denierfiber such as microfiber can be dyed in deep color relatively easily anda deep bright blue dyed product excellent in various fastness,particularly washing fastness, can be obtained.

The present invention will more concretely explained in reference to thefollowing examples, which are never construed to limit the presentinvention. In the examples, "part" and "%" means "part by weight" and "%by weight", respectively.

EXAMPLE 1

A mixture of 1.69 parts of 2-amino-3-cyano-5-nitrothiophene, 2 parts ofpropionic acid and 8 parts of acetic acid was cooled down to 5° C. orbelow. To the mixture, 2.95 parts of 43% nitrosylsulfuric acid wasdropwise added while keeping the temperature 10° C. or below, followedby stirring the mixture at 5° C. for a while to obtain a diazo solution.

The diazo solution thus obtained was added dropwise to a solution of2.90 parts of 3-ethylsulfonylamino-N,N-diethylaniline and 70 parts ofmethanol. After completion of the dropwise addition, the reactionmixture was stirred for one hour while being cooled with ice toprecipitate a crystalline product, followed by a filtration. Thecrystalline product obtained by the filtration was washed with methanolto obtain a monoazo compound represented by the following formula:##STR9## Solution of the monoazo compound in dimethyl formamide exhibitsblue color and its λ max. was 634 nm.

EXAMPLE 2

1.0 part of monoazo compound obtained in Example 1 together with 3.0parts of a condensation product of naphthalene sulfonic acid andformaldehyde was finely pulverized in aqueous medium, followed by dryingthe dye dispersion to obtain dye powder. To a dye bath containing 0.6part of the dye powder thus obtained, 10 parts of Tetron jersey (apolyester fiber textile manufactured by Toray Co., Ltd.) was dipped anddyeing was carried out for 60 minutes under an elevated pressure at atemperature of 130°-135° C. Thereafter, the dyed product was subjectedto a reduction-rinsing treatment for 10 minutes at a temperature of 85°C. with a solution consisting of 3 parts of sodium hydroxide, 3 parts ofhydrosulfite, 3 parts of betaine type amphoteric surfactant and 3000parts of water, washed with water and dried to obtain a deep brightblue-colored dyed product. The dyed product thus obtained was excellentin light fastness, sublimation fastness and wet fastness.

The dyed product was, then, subjected to softening antistatic finishingaccording the following manner.

A padding liquor containing Sumitex softener LK-1, a softenermanufactured by Sumitomo Chemical Co., Ltd. in a concentration of 10 g/Land Sumistat F-1, an antistatic agent manufactured by Sumitomo ChemicalCo., Ltd. in a concentration of 5 g/L was prepared. In the paddingliquor, the dyed product obtained above was dipped and squeezeduniformly so that the weight-increasing ratio became 80%. Thereafter,the dye product was dipped again, squeezed again similarly, then,subjected to an intermediate drying for 2 minutes at a temperature of80° C., followed by a heat set treatment for a minute at a temperatureof 170° C. Then, washing fastness of the dyed product was measuredaccording to AATCC IIA method. The washing fastness thus measured wasgrade 5.

Comparative Example 1

Example 2 was repeated except that the monoazo compound obtained inExample 1 was replaced by a compound represented by the followingformula ##STR10## which is described in JP-A-48-84120. The dyed productthus obtained exhibits dull blue color. After softening antistaticfinishing, the washing fastness of the dyed product was measuredaccording to AATCC IIA method. The washing fastness thus measured wasgrade 3.

Comparative Example 2

Example 2 was repeated except that the monoazo compound obtained inExample 1 was replaced by a compound represented by the followingformula ##STR11## which is described in JP-A-48-84120. The dyed productthus obtained exhibits dull reddish blue color.

EXAMPLE 3

1.3 parts of monoazo compound obtained in Example 1 was finelypulverized together with 3.7 parts of lignin sulfonic acid, and to theresulting dye dispersion, 35 parts of warm water and 60 parts ofhalf-emulsion paste of the following formulation were added and mixed toprepare a printing paste.

    ______________________________________                                        o/w emulsion      300         parts                                           Mayprogum NP12% paste                                                                           694         parts                                           sodium chlorate   4           parts                                           tartaric acid     2           parts                                           Total             1000        parts                                           ______________________________________                                    

Using the printing paste, Tetron tropical (a polyester fiber textilemanufactured by Toray Co., Ltd.) was printed, dried and, then, subjectedto steaming for 7 minutes under atmospheric pressure at a temperature of170° C. with a high-temperature steamer for fixing the dye. Thereafter,according to the same method as that in Example 2, reduction-rinsingtreatment, washing with water, softening and antistatic finishing werecarried out in the mentioned order to obtain a deep bright blue dyedproduct. The dyed product was excellent in wet fastness, light fastnessand sublimation fastness.

EXAMPLE 4

Example 1 was repeated except that 2.90 parts of3-ethylsulfonylamino-N,N-diethylaniline was replaced by 4.7 parts of3-methylsulfonylamino-N,N- 2-(2-ethoxyethoxy)ethyl! aniline to obtain amonoazo compound represented by the following formula: ##STR12##Solution of the monoazo compound in dimethylformamide exhibits bluecolor, and its λ max. was 630 nm. Then, Example 2 was repeated exceptthat the monoazo compound obtained in Example 1 was replaced by themonoazo compound obtained in this Example. The dyed product thusobtained was excellent in wet fastness, light fastness and sublimationfastness.

EXAMPLE 5

Example 1 was repeated except that 2.90 parts of3-ethylsulfonylamino-N,N-diethylaniline was replaced by 3.5 parts of3-methylsulfonylamino-N-(2-phenoxyethyl) aniline to obtain a monoazocompound represented by the following formula: ##STR13## Solution of themonoazo compound in dimethylformamide exhibits blue color, and its λmax. was 640 nm. Then, Example 2 was repeated except that the monoazocompound obtained in Example 1 was replaced by the monoazo compoundobtained in this Example. The dyed product thus obtained was excellentin wet fastness, light fastness and sublimation fastness.

The light fastness was grade 5 which was evaluated according to JISL0842 by using a carbon arc as the light source. In order to evaluatecolor depth of the dyed product, a measurement of SQ value wasconducted. SQ value is obtained by measuring optical density at eachwave length which was obtained from reflection ratio of natural light(light source : day-light D65) on dyed product with SICOMAC-20 (a colormeasuring apparatus manufactured by Sumika Chemical Analysis Co., Ltd.).SICOMAC-20 is an measuring apparatus equipped with a light source, aspectrometer, a computer for data calculation. SQ value indicatesrelative color densities on the surface of dyed product. The higher theSQ value, the higher the dyeing ability. SQ value of the dyed product inthis Example thus measured was 31.

Comparative Example 3

Example 1 was repeated except that 2.90 parts of3-ethylsulfonylamino-N,N-diethylaniline was replaced by 4.8 parts of3-methylsulfonylamino-N,N-di(2-phenoxyethyl) aniline to obtain a monoazocompound represented by the following formula: ##STR14##

Then, Example 2 was repeated except that the monoazo compound obtainedin Example 1 was replaced by the monoazo compound obtained in thisExample. Dyeablity of the compound and fastness such as light fastnessof the dyed product are insufficient.

The light fastness was grade 3 which was evaluated according to JISL0842by using a carbon arc as the light source. SQ value of the dyedproduct in this Example was 10.

Examples 6-184

Example 1 was repeated except that3-ethylsulfonylamino-N,N-diethylaniline was replaced by 3-N-substitutedamino-alkylsulfonylamino benzene or 3-N-substitutedamino-phenylsulfonylamino benzene represented by the formula(III) inwhich R₂, R₃, R₄ and R₅ are those described in the following Tables 1-14to obtain a monoazo compound having blue color. In the Tables, Ph andTHF mean a phenyl group and a tetrahydrofurfuryl group, respectively.

λ max., light fastness and washing fastness of the monoazo compoundsobtained in Example 11, 16-19, 65 and 181-184 were measured and theresults are shown in Table 15. The washing fastness was measuredaccording to the same manner as in Example 2, i.e. according to AATCCIIA method. The light fastness was measured according to JIS L0842 usinga carbon arc as the light source.

                  TABLE 1                                                         ______________________________________                                        Exp. No.                                                                              R.sub.2 R.sub.3                                                                              R.sub.4    R.sub.5                                     ______________________________________                                         6      CH.sub.3                                                                              H      C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                              7      CH.sub.3                                                                              H      C.sub.2 H.sub.4 OC.sub.3 H.sub.7                                                         C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n)         8      CH.sub.3                                                                              H      C.sub.2 H.sub.4 OC.sub.3 H.sub.7                                                         C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (i)         9      CH.sub.3                                                                              H      n-C.sub.5 H.sub.11                                                                       n-C.sub.5 H.sub.11                          10      CH.sub.3                                                                              H      n-C.sub.3 H.sub.7                                                                        n-C.sub.3 H.sub.7                           11      CH.sub.3                                                                              H      C.sub.2 H.sub.4 OCO.sub.2 C.sub.2 H.sub.5                                                C.sub.2 H.sub.4 OCO.sub.2 C.sub.2                                             H.sub.5                                     12      CH.sub.3                                                                              H      CH.sub.3   CH.sub.3                                    13      CH.sub.3                                                                              H      C.sub.3 H.sub.6 OCO.sub.2 C.sub.2 H.sub.5                                                C.sub.3 H.sub.6 OCO.sub.2 C.sub.2                                             H.sub.5                                     14      CH.sub.3                                                                              H      C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                         C.sub.3 H.sub.6 OC.sub.2 H.sub.5            15      CH.sub.3                                                                              H      C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3                                               C.sub.2 H.sub.4 OC.sub.2 H.sub.4                                              OCH.sub.3                                   16      CH.sub.3                                                                              H      C.sub.2 H.sub.4 OCO.sub.2 CH.sub.3                                                       C.sub.2 H.sub.4 OCO.sub.2 CH.sub.3          17      CH.sub.3                                                                              H      C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5                                                       C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5          18      CH.sub.3                                                                              H      C.sub.2 H.sub.4 OCO.sub.2 C.sub.3 H.sub.7 -n                                             C.sub.2 H.sub.4 OCO.sub.2 C.sub.3                                             H.sub.7 -n                                  19      CH.sub.3                                                                              H      C.sub.2 H.sub.4 OCOC.sub.3 H.sub.7 -n                                                    C.sub.2 H.sub.4 OCOC.sub.3 H.sub.7 -n       20      CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                        C.sub.2 H.sub.4 CO.sub.2 CH.sub.3           ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Exp. No.                                                                              R.sub.2 R.sub.3                                                                              R.sub.4    R.sub.5                                     ______________________________________                                        21      CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 C.sub.3 H.sub.7 -n                                              C.sub.2 H.sub.4 CO.sub.2 C.sub.3                                              H.sub.7 -n                                  22      CH.sub.3                                                                              H      C.sub.2 H.sub.4 CN                                                                       C.sub.2 H.sub.5                             23      CH.sub.3                                                                              H      C.sub.2 H.sub.4 CN                                                                       C.sub.2 H.sub.4 OPh                         24      C.sub.2 H.sub.5                                                                       H      CH.sub.3   CH.sub.3                                    25      C.sub.2 H.sub.5                                                                       H      C.sub.3 H.sub.6 OCO.sub.2 C.sub.2 H.sub.5                                                C.sub.3 H.sub.6 OCO.sub.2 C.sub.2                                             H.sub.5                                     26      C.sub.2 H.sub.5                                                                       H      C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                         C.sub.3 H.sub.6 OC.sub.2 H.sub.5            27      C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3                                               C.sub.2 H.sub.4 OC.sub.2 H.sub.4                                              OCH.sub.3                                   28      C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 OCO.sub.2 CH.sub.3                                                       C.sub.2 H.sub.4 OCO.sub.2 CH.sub.3          29      C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5                                                       C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5          30      C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 OCO.sub.2 C.sub.3 H.sub.7 -n                                             C.sub.2 H.sub.4 OCO.sub.2 C.sub.3                                             H.sub.7 -n                                  31      C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 OCOC.sub.3 H.sub.7 -n                                                    C.sub.2 H.sub.4 OCOC.sub.3 H.sub.7 -n       32      C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 CO.sub.2 C.sub.3 H.sub.7 -n                                              C.sub.2 H.sub.4 CO.sub.2 C.sub.3                                              H.sub.7 -n                                  33      C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                        C.sub.2 H.sub.4 CO.sub.2 CH.sub.3           34      C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 CN                                                                       C.sub.2 H.sub.5                             35      C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 CN                                                                       C.sub.2 H.sub.4 OPh                         36      C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                         C.sub.2 H.sub.4 OC.sub.2 H.sub.5            ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Exp. No.                                                                             R.sub.2 R.sub.3                                                                              R.sub.4     R.sub.5                                     ______________________________________                                        37     C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 OC.sub.3 H.sub.7                                                          C.sub.2 H.sub.4 OC.sub.3 H.sub.7            38     C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                         C.sub.2 H.sub.4 OC.sub.2 H.sub.4                                              OC.sub.2 H.sub.5                            39     C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 OPh                                                                       H                                           40     CH.sub.3                                                                              H      C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.4 OPh                         41     CH.sub.3                                                                              H      C.sub.2 H.sub.4 CN                                                                        C.sub.2 H.sub.4 CN                          42     CH.sub.3                                                                              H      C.sub.2 H.sub.4 OH                                                                        C.sub.2 H.sub.4 OPh                         43     CH.sub.3                                                                              H      C.sub.2 H.sub.4 CN                                                                        C.sub.2 H.sub.4 Ph                          44     CH.sub.3                                                                              H      C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.4 Ph                          45     CH.sub.3                                                                              H      C.sub.2 H.sub.4 Ph                                                                        H                                           46     CH.sub.3                                                                              H      CH.sub.2 Ph C.sub.2 H.sub.5                             47     CH.sub.3                                                                              H      CH.sub.2 CH(OH)CH.sub.2 OPh                                                               H                                           48     CH.sub.3                                                                              H      C.sub.2 H.sub.4 OC.sub.4 H.sub.9 -n                                                       C.sub.2 H.sub.4 OC.sub.4 H.sub.9 -n         49     CH.sub.3                                                                              H      CH.sub.2 CH═CH.sub.2                                                                  CH.sub.2 CH═CH.sub.2                    50     CH.sub.3                                                                              H      C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.4 OCOPh                       51     CH.sub.3                                                                              H      n-C.sub.6 H.sub.13                                                                        n-C.sub.6 H.sub.13                          52     CH.sub.3                                                                              H      C.sub.2 H.sub.5                                                                           C.sub.4 H.sub.8 OCOCH.sub.3                 ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                        Exp.                                                                          No.   R.sub.2                                                                              R.sub.3 R.sub.4     R.sub.5                                      ______________________________________                                        53    CH.sub.3                                                                             H       n-C.sub.4 H.sub.9                                                                         CH.sub.2 CH.sub.2 CH.sub.2 Ph                54    CH.sub.3                                                                             OCH.sub.3                                                                             C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                              55    CH.sub.3                                                                             OC.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                              56    Ph     H       C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.5                              57    Ph     H       C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                         C.sub.2 H.sub.4 OC.sub.2 H.sub.4                                              OC.sub.2 H.sub.5                             58    Ph     H       C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                          C.sub.2 H.sub.4 OC.sub.2 H.sub.5             59    Ph     H       C.sub.2 H.sub.4 OCO.sub.2 CH.sub.3                                                        C.sub.2 H.sub.4 OCO.sub.2 CH.sub.3           60    Ph     H       C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5                                                        C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5           61    Ph     H       C.sub.2 H.sub.4 OCO.sub.2 C.sub.3 H.sub.7 -n                                              C.sub.2 H.sub.4 OCO.sub.2 C.sub.3                                             H.sub.7 -n                                   62    Ph     H       C.sub.2 H.sub.4 OCOC.sub.3 H.sub.7 -n                                                     C.sub.2 H.sub.4 OCOC.sub.3 H.sub.7 -n        63    CH.sub.3                                                                             OCH.sub.3                                                                             C.sub.2 H.sub.4 CN                                                                        C.sub.2 H.sub.4 CN                           64    CH.sub.3                                                                             OCH.sub.3                                                                             C.sub.2 H.sub.4 OCH.sub.3                                                                 C.sub.2 H.sub.4 OCH.sub.3                    65    CH.sub.3                                                                             H       C.sub.2 H.sub.4 OCOCH.sub.3                                                               C.sub.2 H.sub.4 OCOCH.sub.3                  66    Ph     H       C.sub.2 H.sub.4 OH                                                                        C.sub.2 H.sub.4 CN                           67    CH.sub.3                                                                             H                                                                                      ##STR15##                                                                                 ##STR16##                                   68    CH.sub.3                                                                             H       H                                                                                          ##STR17##                               

    TABLE 5                                                                       ______________________________________                                        Exp. No.                                                                             R.sub.2                                                                              R.sub.3                                                                              R.sub.4     R.sub.5                                      ______________________________________                                        69     CH.sub.3                                                                             H      CH.sub.2 CO.sub.2 CH.sub.3                                                                CH.sub.2 CO.sub.2 CH.sub.3                   70     CH.sub.3                                                                             H      C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OC.sub.2                             H.sub.5     H                                            71     CH.sub.3                                                                             H      C.sub.3 H.sub.6 CO.sub.2 C.sub.2 H.sub.5                                                  C.sub.3 H.sub.6 CO.sub.2 C.sub.2                                              H.sub.5                                      72     CH.sub.3                                                                             H      CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                         CH.sub.2 CO.sub.2 C.sub.2 H.sub.5            73     CH.sub.3                                                                             H      C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OCH.sub.3                                        C.sub.2 H.sub.5                              74     CH.sub.3                                                                             H      CH.sub.2 CO.sub.2 C.sub.3 H.sub.7 -n                                                      CH.sub.2 CO.sub.2 C.sub.3 H.sub.7 -n         75     CH.sub.3                                                                             H      C.sub.3 H.sub.6 CO.sub.2 CH.sub.3                                                         C.sub.3 H.sub.6 CO.sub.2 CH.sub.3            76     CH.sub.3                                                                             H      C.sub.2 H.sub.4 CO.sub.2 -THF                                                             CH.sub.3                                     77     CH.sub.3                                                                             H      C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OC.sub.2                             H.sub.4     C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4                                      OC.sub.2 H.sub.4                             78     CH.sub.3                                                                             H      C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                         C.sub.2 H.sub.5                              79     CH.sub.3                                                                             H      C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OC.sub.2                             H.sub.5     C.sub.2 H.sub.5                              80     CH.sub.3                                                                             H      C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OCH.sub.3                                        H                                            ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                        Exp. No.                                                                              R.sub.2 R.sub.3                                                                              R.sub.4    R.sub.5                                     ______________________________________                                        81      CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 --THF                                                           H                                           82      CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.5                                                 C.sub.2 H.sub.4 CO.sub.2 C.sub.2                                              H.sub.5                                     83      CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 C.sub.3 H.sub.7 -n                                              CH.sub.3                                    84      CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.5                                                 C.sub.2 H.sub.5                             85      CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                        C.sub.3 H.sub.7 -n                          86      CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.5                                                 C.sub.4 H.sub.9 -n                          87      CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.5                                                 CH.sub.3                                    88      CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                        H                                           89      CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 C.sub.3 H.sub.7 -n                                              C.sub.3 H.sub.7 -n                          90      CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 C.sub.4 H.sub.9 -n                                              C.sub.2 H.sub.5                             91      CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.5                                                 H                                           ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                        Exp. No.                                                                             R.sub.2                                                                              R.sub.3                                                                             R.sub.4     R.sub.5                                       ______________________________________                                        92     CH.sub.3                                                                             H     C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.5                                                  C.sub.2 H.sub.4 OC.sub.2 H.sub.5              93     CH.sub.3                                                                             H     C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.5                                                  C.sub.3 H.sub.7 -n                            94     CH.sub.3                                                                             H     C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OCH.sub.3                                        C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4                                      OCH.sub.3                                     95     CH.sub.3                                                                             H     C.sub.2 H.sub.4 CO.sub.2 C.sub.3 H.sub.7 -n                                               H                                             96     CH.sub.3                                                                             H     C.sub.2 H.sub.4 CO.sub.2 --THF                                                            C.sub.2 H.sub.5                               97     CH.sub.3                                                                             H     C.sub.2 H.sub.4 CO.sub.2 C.sub.3 H.sub.7 -n                                               C.sub.2 H.sub.5                               98     CH.sub.3                                                                             H     C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.5                                                  C.sub.2 H.sub.4 OCH.sub.3                     99     CH.sub.3                                                                             H     C.sub.2 H.sub.4 CO.sub.2 C.sub.4 H.sub.9 -n                                               H                                             100    CH.sub.3                                                                             H     C.sub.2 H.sub.4 CO.sub.2 --THF                                                            C.sub.2 H.sub.4 CO.sub.2 --THF                101    CH.sub.3                                                                             H     C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                         C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2                                     H.sub.5                                       102    CH.sub.3                                                                             H     C.sub.2 H.sub.4 OPh                                                                       C.sub.4 H.sub.9 -n                            ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                        Exp. No.                                                                              R.sub.2                                                                              R.sub.3                                                                              R.sub.4     R.sub.5                                     ______________________________________                                        103     CH.sub.3                                                                             H      C.sub.2 H.sub.4 OPh                                                                       C.sub.2 H.sub.4 CO.sub.2 C.sub.2                                              H.sub.5                                     104     CH.sub.3                                                                             H      C.sub.2 H.sub.4 OPh                                                                       CH.sub.3                                    105     CH.sub.3                                                                             H      CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                         C.sub.2 H.sub.4 OPh                         106     CH.sub.3                                                                             H      C.sub.2 H.sub.4 CO.sub.2 C.sub.2 H.sub.4 OCH.sub.3                                        C.sub.2 H.sub.4 OPh                         107     CH.sub.3                                                                             H      C.sub.3 H.sub.7 -n                                                                        C.sub.2 H.sub.4 OPh                         108     CH.sub.3                                                                             H      C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                          C.sub.2 H.sub.4 OPh                         109     CH.sub.3                                                                             H      C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                         C.sub.2 H.sub.4 OPh                         110     CH.sub.3                                                                             H      C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                         H                                           111     CH.sub.3                                                                             H      C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                          H                                           112     CH.sub.3                                                                             H      C.sub.2 H.sub.4 OPh                                                                       CH.sub.2 OC.sub.3 H.sub.7 -n                113     CH.sub.3                                                                             H      C.sub.2 H.sub.4 OPh                                                                       C.sub.2 H.sub.4 CO.sub.2 C.sub.3                                              H.sub.7 -n                                  114     CH.sub.3                                                                             H      C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5                                                        C.sub.2 H.sub.4 OPh                         ______________________________________                                    

                  TABLE 9                                                         ______________________________________                                        Exp. No.                                                                             R.sub.2 R.sub.3                                                                              R.sub.4     R.sub.5                                     ______________________________________                                        115    CH.sub.3                                                                              H      C.sub.2 H.sub.4 OC.sub.4 H.sub.9 -n                                                       C.sub.2 H.sub.4 OPh                         116    CH.sub.3                                                                              H      C.sub.2 H.sub.4 OPh                                                                       C.sub.2 H.sub.4 CO.sub.2 --THF              117    CH.sub.3                                                                              H      C.sub.2 H.sub.4 OPh                                                                       C.sub.2 H.sub.4 OCOC.sub.3 H.sub.7 -n       118    CH.sub.3                                                                              H      C.sub.2 H.sub.4 OPh                                                                       C.sub.2 H.sub.4 OCH.sub.3                   119    CH.sub.3                                                                              H      C.sub.4 H.sub.8 (n)-OC.sub.2 H.sub.5                                                      C.sub.2 H.sub.4 OPh                         120    CH.sub.3                                                                              H      C.sub.2 H.sub.4 OCOOC.sub.2 H.sub.5                                                       C.sub.2 H.sub.4 OPh                         121    CH.sub.3                                                                              H      C.sub.2 H.sub.4 OC.sub.3 H.sub.7 -n                                                       C.sub.2 H.sub.4 OPh                         122    CH.sub.3                                                                              H      C.sub.2 H.sub.4 OPh                                                                       C.sub.2 H.sub.4 OCOOCH.sub.3                123    CH.sub.3                                                                              H      C.sub.2 H.sub.4 OPh                                                                       C.sub.3 H.sub.6 OCH.sub.3                   124    CH.sub.3                                                                              H      C.sub.2 H.sub.4 OCOOC.sub.3 H.sub.7 -n                                                    C.sub.2 H.sub.4 OPh                         125    CH.sub.3                                                                              H      C.sub.2 H.sub.4 OPh                                                                       C.sub.2 H.sub.4 OCOCH.sub.3                 ______________________________________                                    

                  TABLE 10                                                        ______________________________________                                        Exp. No.                                                                             R.sub.2 R.sub.3                                                                              R.sub.4    R.sub.5                                      ______________________________________                                        126    CH.sub.3                                                                              H      C.sub.3 H.sub.7 -i                                                                       C.sub.3 H.sub.7 -i                           127    CH.sub.3                                                                              H      C.sub.2 H.sub.5                                                                          H                                            128    CH.sub.3                                                                              H      H          C.sub.5 H.sub.11 -n                          129    CH.sub.3                                                                              H      C.sub.2 H.sub.4 OH                                                                       C.sub.2 H.sub.4 OH                           130    CH.sub.3                                                                              H      C.sub.2 H.sub.4 OCH.sub.3                                                                C.sub.2 H.sub.4 OCH.sub.3                    131    CH.sub.3                                                                              H      C.sub.3 H.sub.6 OCH.sub.3                                                                C.sub.3 H.sub.6 OCH.sub.3                    132    CH.sub.3                                                                              H      C.sub.4 H.sub.8 (n)-OCH.sub.3                                                            C.sub.4 H.sub.8 (n)-OCH.sub.3                133    CH.sub.3                                                                              H      C.sub.6 H.sub.12 (n)-OCH.sub.3                                                           C.sub.6 H.sub.12 (n)-OCH.sub.3               134    CH.sub.3                                                                              H      C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                         C.sub.2 H.sub.5                              135    CH.sub.3                                                                              H      C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.4 OC.sub.2 H.sub.4                                              OC.sub.2 H.sub.5                             136    CH.sub.3                                                                              H      C.sub.5 H.sub.11 -n                                                                      C.sub.2 H.sub.4 OCH.sub.3                    137    CH.sub.3                                                                              H      C.sub.2 H.sub.4 OC.sub.4 H.sub.9 -n                                                      C.sub.2 H.sub.5                              ______________________________________                                    

                  TABLE 11                                                        ______________________________________                                        Exp. No.                                                                              R.sub.2                                                                              R.sub.3                                                                              R.sub.4    R.sub.5                                      ______________________________________                                        138     CH.sub.3                                                                             H      C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                         CH.sub.3                                     139     CH.sub.3                                                                             H      C.sub.3 H.sub.7 -n                                                                       C.sub.2 H.sub.4 OCH.sub.3                    140     CH.sub.3                                                                             H      CH.sub.3   C.sub.2 H.sub.4 OC.sub.2 H.sub.4                                              OC.sub.2 H.sub.5                             141     CH.sub.3                                                                             H      C.sub.2 H.sub.4 CN                                                                       C.sub.2 H.sub.4 OCOPh                        142     CH.sub.3                                                                             H      C.sub.4 H.sub.8 (n)-OCOOCH.sub.3                                                         C.sub.4 H.sub.8 (n)-OCOOCH.sub.3             143     CH.sub.3                                                                             H      C.sub.2 H.sub.4 OCOOC.sub.2 H.sub.5                                                      C.sub.2 H.sub.4 OH                           144     CH.sub.3                                                                             H      C.sub.2 H.sub.4 CN                                                                       C.sub.2 H.sub.4 OCOOPh                       145     CH.sub.3                                                                             H      C.sub.2 H.sub.4 OH                                                                       C.sub.2 H.sub.4 OCOC.sub.2 H.sub.5           146     Ph     H      CH.sub.3   CH.sub.3                                     147     Ph     H      C.sub.2 H.sub.4 OCOOC.sub.2 H.sub.5                                                      H                                            148     Ph     H      C.sub.6 H.sub.13 -n                                                                      C.sub.6 H.sub.13 -n                          149     Ph     H      C.sub.2 H.sub.4 COCH.sub.3                                                               C.sub.2 H.sub.4 COCH.sub.3                   ______________________________________                                    

                  TABLE 12                                                        ______________________________________                                        Exp. No.                                                                             R.sub.2                                                                              R.sub.3                                                                             R.sub.4      R.sub.5                                      ______________________________________                                        150    Ph     H     C.sub.2 H.sub.4 COC.sub.2 H.sub.5                                                          H                                            151    Ph     H     C.sub.4 H.sub.9 -n                                                                         C.sub.4 H.sub.9 -n                           152    Ph     H     CH.sub.3     C.sub.2 H.sub.4 OPh                          153    Ph     H     C.sub.2 H.sub.4 COC.sub.2 H.sub.5                                                          C.sub.2 H.sub.4 COC.sub.2 H.sub.5            154    Ph     H     H            C.sub.2 H.sub.4 OCOCH.sub.3                  155    Ph     H     C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.4 OPh                          156    Ph     H     C.sub.2 H.sub.4 COCH.sub.3                                                                 C.sub.2 H.sub.5                              157    Ph     H     C.sub.2 H.sub.4 OPh                                                                        H                                            158    Ph     H     C.sub.2 H.sub.4 COOC.sub.2 H.sub.4 OCH.sub.3                                               CH.sub.3                                     159    Ph     H     H            C.sub.2 H.sub.4 COCH.sub.3                   160    Ph     H     H            C.sub.2 H.sub.4 COOC.sub.2 H.sub.4                                            OCH.sub.3                                    ______________________________________                                    

                  TABLE 13                                                        ______________________________________                                        Exp. No.                                                                             R.sub.2 R.sub.3                                                                              R.sub.4    R.sub.5                                      ______________________________________                                        161    CH.sub.3                                                                              H      C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                         C.sub.2 H.sub.4 OC.sub.2 H.sub.5             162    CH.sub.3                                                                              H      C.sub.2 H.sub.4 CN                                                                       C.sub.2 H.sub.4 OC.sub.2 H.sub.4                                              OC.sub.2 H.sub.5                             163    CH.sub.3                                                                              H      C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OPh                                                     C.sub.2 H.sub.4 CN                           164    C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 OCOCH.sub.3                                                              C.sub.2 H.sub.4 OPh                          165    C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 OCOOC.sub.2 H.sub.5                                                      C.sub.2 H.sub.4 OCOOC.sub.2 H.sub.5          166    C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 COOC.sub.2 H.sub.5                                                       C.sub.2 H.sub.4 COOC.sub.2 H.sub.5           167    C.sub.2 H.sub.5                                                                       H      C.sub.3 H.sub.7 -n                                                                       C.sub.2 H.sub.4 COOCH.sub.3                  168    C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 CN                                                                       C.sub.2 H.sub.4 OCOOC.sub.2 H.sub.5          169    C.sub.2 H.sub.5                                                                       H      H          C.sub.2 H.sub.4 COOC.sub.2 H.sub.5           170    C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 OCOOC.sub.2 H.sub.5                                                      C.sub.2 H.sub.4 OPh                          171    C.sub.2 H.sub.5                                                                       H      H          CH.sub.2 COOC.sub.2 H.sub.5                  172    C.sub.2 H.sub.5                                                                       H      C.sub.2 H.sub.4 COOC.sub.2 H.sub.5                                                       C.sub.2 H.sub.5                              ______________________________________                                    

                  TABLE 14                                                        ______________________________________                                        Exp. No.                                                                             R.sub.2                                                                              R.sub.3                                                                             R.sub.4      R.sub.5                                      ______________________________________                                        173    C.sub.2 H.sub.5                                                                      H     CH.sub.2 COOC.sub.2 H.sub.5                                                                CH.sub.2 COOC.sub.2 H.sub.5                  174    C.sub.2 H.sub.5                                                                      H     C.sub.2 H.sub.4 COOC.sub.2 H.sub.4 OCH.sub.3                                               C.sub.2 H.sub.5                              175    C.sub.2 H.sub.5                                                                      H     C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                          C.sub.2 H.sub.4 OPh                          176    C.sub.2 H.sub.5                                                                      H     H            C.sub.2 H.sub.4 COOC.sub.2 H.sub.4                                            OCH.sub.3                                    177    C.sub.2 H.sub.5                                                                      H     C.sub.2 H.sub.4 COO--THF                                                                   H                                            178    C.sub.2 H.sub.5                                                                      H     C.sub.2 H.sub.4 COOC.sub.2 H.sub.4 OCH.sub.3                                               C.sub.2 H.sub.4 COOC.sub.2 H.sub.4                                            OCH.sub.3                                    179    C.sub.2 H.sub.5                                                                      H     C.sub.2 H.sub.4 OPh                                                                        C.sub.2 H.sub.4 OC.sub.2 H.sub.5             180    C.sub.2 H.sub.5                                                                      H     CH.sub.2 COOCH.sub.3                                                                       C.sub.2 H.sub.5                              181    CH.sub.3                                                                             H     C.sub.2 H.sub.4 OCO.sub.2 C.sub.4 H.sub.9 -n                                               C.sub.2 H.sub.4 OCO.sub.2 C.sub.4                                             H.sub.9 -n                                   182    CH.sub.3                                                                             H     C.sub.2 H.sub.4 OCO.sub.2 C.sub.5 H.sub.11 -n                                              C.sub.2 H.sub.4 OCO.sub.2 C.sub.5                                             H.sub.11 -n                                  183    CH.sub.3                                                                             H     C.sub.2 H.sub.4 OCOC.sub.4 H.sub.9 -n                                                      C.sub.2 H.sub.4 OCOC.sub.4 H.sub.9 -n        184    CH.sub.3                                                                             H     C.sub.2 H.sub.4 OCOC.sub.5 H.sub.11 -n                                                     C.sub.2 H.sub.4 OCOC.sub.5 H.sub.11          ______________________________________                                                                         -n                                       

                  TABLE 15                                                        ______________________________________                                                           Light Fastness                                                                           Washing Fastness                                Exp. No. λmax                                                                             (grade)    (grade)                                         ______________________________________                                        11       623 nm    4-5        4-5                                             16       623 nm    4-5        5                                               17       623 nm    4-5        5                                               18       623 nm    4-5        5                                               19       623 nm    4-5        4-5                                             65       623 nm    4-5        5                                               181      623 nm    4-5        5                                               182      623 nm    4-5        5                                               183      623 nm    4-5        5                                               184      623 nm    4-5        5                                               ______________________________________                                    

According to same procedures as in Example 1 except that3-ethylsulfonylamino-N,N-diethylaniline was replaced by 3-N-substitutedamino-alkylsulfonylamino benzene represented by the formula(III) inwhich R₂, R₃, R₄ and R₅ are those described in the following Table 16, amonoazo compound having blue color can be obtained.

                  TABLE 16                                                        ______________________________________                                        Exp. No.                                                                             R.sub.2 R.sub.3                                                                              R.sub.4     R.sub.5                                     ______________________________________                                        185    CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                         C.sub.4 H.sub.9 -n                          186    CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 --C.sub.3 H.sub.7 -n                                             C.sub.4 H.sub.9 -n                          187    CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 C.sub.4 H.sub.9 -n                                               C.sub.4 H.sub.9 -n                          188    CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 C.sub.4 H.sub.9 -n                                               C.sub.3 H.sub.7 -n                          189    CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 C.sub.4 H.sub.9 -n                                               CH.sub.3                                    190    CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 C.sub.4 H.sub.9 -n                                               C.sub.2 H.sub.4 CO.sub.2 C.sub.4                                              H.sub.9 -n                                  191    CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                         C.sub.6 H.sub.13 -n                         192    CH.sub.3                                                                              H      C.sub.2 H.sub.4 CO.sub.2 CH.sub.3                                                         C.sub.5 H.sub.11 -n                         ______________________________________                                    

What we claim is:
 1. A monoazo compound represented by the followingformula (I): ##STR18## wherein R₁ represents a hydrogen atom or achlorine atom; R₂ represents a phenyl group or a straight chain orbranched chain alkyl group which is unsubstituted or substituted; R₃ isa hydrogen atom or C₁ -C₄ alkoxy; and R₄ and R₅, which are same ordifferent, represent a hydrogen atom, an allyl group, atetrahydrofurfuryl group, or a straight chain or branched chain C₁ -C₆alkyl group which is unsubstituted or substituted by one or twosubstituents selected from a chlorine atom, a bromine atom, a cyanogroup, an alkoxy group, a phenoxyalkoxy group, a phenoxy group, a phenylgroup, a benzyloxy group, an alkoxycarbonyl group, an alkoxycarbonyloxygroup, an alkanoyloxy group, a benzoyloxy group, a phenoxycarbonyloxygroup, an alkanoyl group, an alkoxyalkoxycarbonyl group, atetrahydrofurfuryloxy carbonyl group and an alkoxyalkoxy group; providedthat R₄ and R₅ are not simultaneously hydrogen atoms, and that R₄ and R₅are not simultaneously straight chain or branched chain C₁ -C₆ alkylgroups which are substituted by one or two substituents selected from aphenoxyalkoxy group, a phenoxy group, a phenyl group, a benzyloxy group,a benzoyloxy group, a phenoxycarbonyloxy group, an alkoxycarbonyl group,an alkoxycarbonyloxy group, and alkanoyloxy group, analkoxyalkoxycarbonyl group, a tetrahydrofurfuryloxycarbonyl group and acyano group.
 2. A monoazo compound according to claim 1 wherein R₁ is ahydrogen atom.
 3. A monoazo compound according to claim 1 wherein R₄ andR₅, which are same or different, are a hydrogen atom; an allyl group; atetrahydrofurfuryl group; or a straight chain or branched chain C₁ -C₆alkyl group which is unsubstituted or substituted by one or twosubstituents selected from a cyano group, a C₁ -C₄ alkoxy group, ahydroxy group, a phenoxyalkoxy group, a phenoxy group, a phenyl group, aC₂ -C₅ alkanoyloxy group, a benzoyloxy group, a C₂ -C₅ alkoxycarbonylgroup, a C₂ -C₅ alkoxycarbonyloxy group, a phenoxycarbonyloxy group, analkoxyalkoxycarbonyl group in which each of the alkoxy groups has one tofour carbon atoms, an alkoxyalkoxy group in which each of the alkoxygroups has one to four carbon atoms and a tetrahydrofurfuryloxy carbonylgroup.
 4. A monoazo compound according to claim 3 wherein R₄ and R₅,which are same or different, are a hydrogen atom; an allyl group; atetrahydrofurfuryl group; or a straight chain or branched chain C₁ -C₆alkyl group which is unsubstituted or substituted by one or twosubstituents selected from a cyano group, a C₁ -C₄ alkoxy group, ahydroxy group, a C₂ -C₅ alkoxycarbonyl group, a C₂ -C₅ alkoxycarbonyloxygroup, a C₂ -C₅ alkanoyloxy group, a phenoxy group, analkoxyalkoxycarbonyl group in which each of the alkoxy groups has one tofour carbon atoms, an alkoxyalkoxy group in which each of the alkoxygroups has one to four carbon atoms, and a tetrahydrofurfuryloxycarbonyl group.
 5. A monoazo compound according to claim 1 wherein R₂ isa phenyl group or a straight chain or branched chain C₁ -C₄ alkyl group.6. A monoazo compound according to claim 1 wherein R₂ is a phenyl group,a methyl group or an ethyl group.
 7. A monoazo compound according toclaim 1 wherein R₃ is a hydrogen atom.
 8. A method for dyeing orprinting hydrophobic fiber materials which comprises a step applying amonoazo compound according to claim 1 to the hydrophobic fibermaterials.